The first total syntheses of schilancitrilactones B and C have been accomplished in 17 steps (longest linear sequence) from commercially available materials. Key steps include an intramolecular radical cyclization to provide the seven-membered ring, late-stage iodination, and an intermolecular radical addition reaction to complete the total synthesis.Schilancitrilactones B and C (1 and 2; Figure 1) [1] were isolated in 2012 by Sun and co-workers from the stems of Schisandra Lancifolia, which have been used in traditional Chinese medicine for the treatment of neurasthenia and related diseases.[2] Preliminary biological assays indicated that schilancitrilactone C showed biological activities for inhibiting HIV-1 while schilancitrilactone B was not bioactive. The structures of these compounds were striking in that they contain a 5/7/5/5/5-fused pentacyclic ring system bearing nine stereogenic centers. In addition, the three cis-fused fivemembered rings (rings C-E), all with the envelope conformations, and seven contiguous chiral centers (including two quaternary centers) form a structurally rigid tricyclic ring system. Construction of these highly oxygenated unique motifs remains challenging. Herein, we present the first total synthesis of schilancitrilactones B and C. The key steps include the successful implementation of an intramolecular radical cyclization to prepare a seven-member ring, late-stage iodination, and an intermolecular radical CÀC bond formation.